Progress in Solid State Chemistry最新文献

{"title":"Pressure-induced stereochemistry and lone pair (E) localization in BiF3: Ellipsoidal EBi 6s2 / EF 2s2 volumes, perichoresis, and phase transitions","authors":"Samir F. Matar ,&nbsp;Alicia Castro ,&nbsp;Jean Galy","doi":"10.1016/j.progsolidstchem.2025.100550","DOIUrl":"10.1016/j.progsolidstchem.2025.100550","url":null,"abstract":"<div><div>This original work investigates the high-pressure behavior of BiF₃ polymorphs, with emphasis on the stereochemical activity and spatial localization of the 6s² lone electron pair (E) of Bi³⁺and the 2 s² Es of fluoride anions. Using density functional theory (DFT) and electron localization function (ELF) analyses, we characterize the evolution of α-, β-, and γ-BiF₃E polymorphs and report two novel high-pressure phases, δ-BiF₃E and κ-BiF₃E, stabilized at approximately 70 GPa and above 200 GPa, respectively. The β-phase undergoes a clear phase transition near 70 GPa, where structural gliding of fluorine layers induces a symmetry shift from <em>Pnma</em> to <em>Cmcm</em> space group, corresponding to the δ-BiF₃E phase. The δ-phase features a base-centered orthorhombic framework with perichoretic localization of the Bi 6s² lone pair in multiple spatial positions. At pressures exceeding 200 GPa, a previously unobserved polymorph, κ-BiF₃E, emerges with a penta-capped triangular antiprismatic coordination environment and a distorted screw-axis symmetry.</div><div>In this paper “perichoresis” is introduced as an original conceptual tool to describe the simultaneous localization of lone pairs in multiple spatial domains without invoking electronic delocalization.</div><div>The results provide insight into the high-pressure stereochemistry of heavy p-block compounds and offer a predictive model for lone pair behavior under compression.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"80 ","pages":"Article 100550"},"PeriodicalIF":10.5,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145568439","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Insight into Bi-Sb alloys and their chalcogenide compounds for sodium/potassium ion battery (SIB/PIB) anodes","authors":"Defei Li,&nbsp;Ming-Chun Zhao,&nbsp;Tong Yuan,&nbsp;Ke Cui,&nbsp;Fuqin Zhang","doi":"10.1016/j.progsolidstchem.2025.100545","DOIUrl":"10.1016/j.progsolidstchem.2025.100545","url":null,"abstract":"<div><div>Sodium/potassium ion batteries (SIBs/PIBs), emerging as promising alternatives to lithium-ion batteries (LIBs), show great potential in large-scale electrical energy storage systems owing to their abundant reserves, potential cost advantages, and low standard redox potentials. In recent years, Bi-Sb alloys and their chalcogenide compounds (sulfides, selenides, and tellurides) have garnered significant attention due to their unique bimetallic synergistic effects and tunable energy storage mechanisms. This paper reviews the recent progress in Bi-Sb alloys and their chalcogenide compounds as anode materials for SIBs and PIBs. Highlighting the synergistic effects of Bi-Sb systems, the study emphasizes their high theoretical capacity, reduced volume expansion, and enhanced structural stability compared to monometallic counterparts. Key strategies such as nano-structuring (e.g., nanoporous and 2D layered architectures), composite engineering (e.g., carbon-based matrices), and heterostructure design are discussed to address challenges like electrode pulverization. The electrochemical mechanisms, including multi-step alloying and conversion reactions, are analyzed to elucidate performance enhancements in terms of cycling stability, rate capability, and capacity retention. Specifically, the paper examines the structural properties, modification strategies, and performance optimization mechanisms of these materials, and identifies key pathways for their engineering applications, aiming to provide theoretical support and technological references for designing high-capacity anode materials for SIBs/PIBs. Additionally, critical issues, challenges, and prospects for further development are suggested. This work provides critical insights into material design principles and offers pathways for developing next-generation, cost-effective energy storage technologies.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"80 ","pages":"Article 100545"},"PeriodicalIF":10.5,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145005038","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Temperature-induced structural phase transitions in inorganic compounds: symmetry and information-entropy analysis","authors":"Sergey V. Krivovichev","doi":"10.1016/j.progsolidstchem.2025.100547","DOIUrl":"10.1016/j.progsolidstchem.2025.100547","url":null,"abstract":"<div><div>The tendency of crystal-structure symmetry increasing under increasing temperature (also known as a ‘Landau rule’) is one of the major empirical observations with regard to the temperature-induced phase transitions. The validity of the rule was investigated by means of the statistical analysis of the 502 temperature-driven phase transitions in inorganic compounds with known crystal-structure information for all polymorphs. The analysis was performed from the viewpoint of symmetry considerations (that is, the analysis in terms of the crystal-system hierarchy, where cubic system is the highest and triclinic is the lowest) and information-entropy calculations. It was revealed that the information-based structural complexity parameters (most importantly, the total information content per reduced unit cell) are more sensitive structural symmetry indicators than the symmetry classification in terms of the crystal-system hierarchy. The information-entropy measures decrease under increasing temperature in more than 77 % of phase transitions under consideration, which corresponds to the overall rise of symmetry under heating (the ‘Landau rule’). In contrast, the simple symmetry analysis confirms the ‘Landau rule’ in 60 % of cases only. The information-based parameters are especially efficient for the cases, when crystal system does not change (most numerous are monoclinic-monoclinic and orthorhombic-orthorhombic transitions). The deviations from the rule of increasing symmetry correspond to: phase transition sequences with intermediate (transitional) structures of high complexity, isosymmetric and reentrant phase transitions, and transitions that involve low-temperature metastable polymorphs. There are some exceptions that cannot be assigned to any of the phase-transition types mentioned above, where symmetry is decreasing under heating. The symmetry breaking results in the decrease in vibrational entropy, which may be considered as a major driving force behind the ‘Landau rule’. However, various phenomena such as formation and breaking of bonds, charge and orbital ordering, stereoactive activity of lone electron pairs, etc., may seriously influence polymorphic transformations under temperature changes.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"80 ","pages":"Article 100547"},"PeriodicalIF":10.5,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046999","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis, structure and properties of substituted cobalt chalcogenides Co7(Se,Te)8","authors":"D.F. Akramov ,&nbsp;N.V. Selezneva ,&nbsp;E.M. Sherokalova ,&nbsp;D.K. Kuznetsov ,&nbsp;V.A. Kazantsev ,&nbsp;N.V. Baranov","doi":"10.1016/j.progsolidstchem.2025.100548","DOIUrl":"10.1016/j.progsolidstchem.2025.100548","url":null,"abstract":"<div><div>For the first time, polycrystalline samples of Co₇(Se_{1–<em>y</em>}Te_<em>y</em>)₈ were synthesized in the entire concentration range (0 ≤ <em>y</em> ≤ 1) and studied by X-ray diffraction, scanning electron microscopy, and by thermal expansion, specific heat capacity and electrical resistivity measurements. Depending on the concentration of tellurium, the solid-phase reaction method (at <em>y</em> &lt; 0.9) and melting method (at <em>y</em> ≥ 0.9) were used to obtain single-phase samples. A change in the crystal structure (<em>P</em>3₁21 → <em>P</em>-3<em>m</em>1 → <em>P</em>6₃/<em>mmc</em> → <em>P</em>-3<em>m</em>1) due to the disordering of vacancies, significant anisotropy of the thermal atomic displacement, and anisotropic lattice expansion have been observed in this system when selenium is substituted with tellurium. According to specific heat measurements, an increase in tellurium concentration is accompanied by a decrease in the electronic specific heat coefficient, which indicates an increase in the metallicity of the system and is confirmed by electrical resistivity data. In substituted compounds using thermal expansion and temperature-dependent X-ray diffraction, spinodal decomposition of samples was detected upon heating. The second phase in dendritic form was observed using scanning electron microscopy on the surface of slowly cooled tellurium-rich sample.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"80 ","pages":"Article 100548"},"PeriodicalIF":10.5,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145109780","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Capping stabilization mechanism of vanadate-stabilized δ-Bi2O3: Experimental and theoretical approaches","authors":"Zhe-Hao Lin ,&nbsp;Yu-Chun Wu","doi":"10.1016/j.progsolidstchem.2025.100549","DOIUrl":"10.1016/j.progsolidstchem.2025.100549","url":null,"abstract":"","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"80 ","pages":"Article 100549"},"PeriodicalIF":10.5,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145358902","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Plate-like NiCo2O4 integrated with g-C3N4 nanostructures for hybrid supercapacitors and green energy technologies","authors":"Ehtisham Umar ,&nbsp;Fozia Shaheen ,&nbsp;M. Waqas Iqbal ,&nbsp;Mohammed T. Alotaibi ,&nbsp;Amel Ayari-Akkari ,&nbsp;Ali Akremi ,&nbsp;Eman Kashita","doi":"10.1016/j.progsolidstchem.2025.100546","DOIUrl":"10.1016/j.progsolidstchem.2025.100546","url":null,"abstract":"<div><div>The development of nanostructured electrode materials for supercapacitors and green energy applications remains a challenging task, particularly in achieving maximum surface area for optimal electrode-electrolyte interaction. In this study, we synthesize interconnected nanostructured NiCo₂O₄/g-C₃N₄ using a cost-effective hydrothermal method. The NiCo₂O₄/g-C₃N₄ nanocomposite undergoes comprehensive characterization to analyze its structural, morphological, and electrochemical properties using various techniques. Electrodes fabricated from the NiCo₂O₄/g-C₃N₄ material exhibit a high specific capacity (Qs) of 203 C/g. Additionally, the as-fabricated asymmetric supercapacitor (ASC) achieves a remarkable energy density (Ed) of 87.3 Wh/kg and a power density (Pd) of 1038 W/kg at 1.4 A/g, with superior cycling performance, retaining 95.04 % of its capacity after 10,000 cycles. Furthermore, we evaluate the modified NiCo₂O₄/g-C₃N₄ electrodes for their electrocatalytic performance in the oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The results indicate that the NiCo₂O₄/g-C₃N₄ electrode exhibits the best OER performance (overpotential (<em>η</em>) = 287 mV and Tafel slope = 121 mV/dec at 10 mA/cm²) and demonstrates excellent HER activity (<em>η</em> = 336 mV and Tafel slope = 93 mV/dec at −10 mA/cm²) with exceptional cyclic stability. This research highlights the potential of NiCo₂O₄/g-C₃N₄ as a promising material for supercapacitor and green energy technology.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"80 ","pages":"Article 100546"},"PeriodicalIF":10.5,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046843","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Recent advance in preparation, applications and color regulation mechanism of cobalt blue pigment","authors":"Hao Yang ,&nbsp;Bin Mu ,&nbsp;Anjie Zhang ,&nbsp;Aiqin Wang","doi":"10.1016/j.progsolidstchem.2025.100535","DOIUrl":"10.1016/j.progsolidstchem.2025.100535","url":null,"abstract":"<div><div>Cobalt blue (CoAl₂O₄) pigment is a well-known high-end blue inorganic pigment with a spinel structure, and it is irreplaceable in the blue pigments either inorganic or organic ones due to its strong coloring performance, desirable blue chroma, and excellent chemical stability. Therefore, a series of strategies have been developed for the preparation of CoAl₂O₄ pigment including common solid-phase method, liquid-phase and gas-phase technologies to meet the requirements of different application fields. However, the relevant applications of CoAl₂O₄ pigment are restricted at a certain degree due to the high cost derived from the scarcity of cobalt sources as well as the aggregation of CoAl₂O₄ particles during the high-temperature crystallization process. Interestingly, incorporation of stable inorganic substrates facilitates the decrease in the production cost and the control of the size and blue intensity of CoAl₂O₄ nanoparticles, especially incorporation of natural or waste nonmetallic mineral resources. Therefore, this review provides an overview of the recent advance in the synthesis, relevant applications and color regulation mechanism of CoAl₂O₄ pigment combining with the literatures and our research achievements. It is mainly focused on the synthesis mechanism of different methods, and the relationships between the structures and the application performances, especially the structural composition and color performance of the designed CoAl₂O₄/silicate hybrid pigments. Finally, several suggestions are proposed for the future development trend on CoAl₂O₄ pigment and even other eco-friendly inorganic pigments.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"79 ","pages":"Article 100535"},"PeriodicalIF":9.1,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144253807","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rare earth doped Zirconia: Structure, physicochemical properties and recent advancements in technological applications","authors":"S. Kalaivani,&nbsp;M. Ezhilan,&nbsp;M. Deepa,&nbsp;S. Kannan","doi":"10.1016/j.progsolidstchem.2025.100524","DOIUrl":"10.1016/j.progsolidstchem.2025.100524","url":null,"abstract":"<div><div>Zirconia (ZrO₂) based ceramics have been pivotal in the evolution of materials across various applications. Particularly, rare earth (RE) doped ZrO₂ is of greater interest due to its remarkable thermal stability, mechanical strength, and ionic conductivity, which are primarily influenced by its distinct solid state properties. This review aims to deliver a comprehensive analysis of the structural features induced by RE doping, with a particular emphasis on the phase transitions and stability of the various polymorphs of ZrO₂. The relationship between the ionic size of RE, oxygen vacancies and microstructural behavior is explored in the context of lattice distortion and thermodynamic stabilization. The review highlights the critical role of doping strategies in the varying microstructure and enhancing the performance of ZrO₂ based materials. Emerging applications such as solid oxide fuel cells, thermal barrier coatings, bioceramics and optical devices necessitate a comprehensive understanding of fundamental solid state properties to ensure their effective operation. Additionally, future research directions are suggested to facilitate the development of next generation ZrO₂ based systems, with a focus on enhancing their structural and functional performance.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"79 ","pages":"Article 100524"},"PeriodicalIF":9.1,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144204454","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cation substitution enabled electron rearrangement in high-entropy perovskite oxides for enhanced supercapacitor performance","authors":"Xiaoying Hu,&nbsp;Bo Wang,&nbsp;Xiaotong Zhou,&nbsp;Junzhi Li","doi":"10.1016/j.progsolidstchem.2025.100536","DOIUrl":"10.1016/j.progsolidstchem.2025.100536","url":null,"abstract":"<div><div>The controllable synthesis of high-entropy perovskite oxides and the modulation of their electronic structures are crucial for enhancing the electrochemical performance of supercapacitors. However, it remains challenging to regulate the electronic configuration of B-site elements via A-site doping. In this study, we have reconstructed the electron configuration of B-site elements in high-entropy perovskites through Sm doping, and obtained high-entropy perovskite oxides La_1-xSm_x (Mn_0·2Fe_0·2Co_0·2Ni_0·2Cr_0.2)O₃ (LaSmTMO₃−x) with abundant valence states. The fabricated LaSmTMO₃−0.2 exhibits high specific capacitance of 1367.3 F g⁻¹ at 0.5 A g⁻¹. Besides, the asymmetric supercapacitor (ASC) based on LaSmTMO₃−0.2 exhibits an impressive energy density of 41.2 Wh kg⁻¹ at a power density of 400 W kg⁻¹, with a specific capacity retention of 87.1 % after 10000 cycles. The experimental results demonstrate that superior supercapacitor performance can be attributed to electron rearrangement induced by Sm doping, leading to the formation of active metal species with multiple oxidation states. Simultaneously, Sm doping significantly improves structural integrity, electronic conductivity, and ion transfer kinetics. This work emphasizes the importance of A-site regulation of high entropy perovskite oxides for improving electrochemical performance and provides A new direction for the design of perovskite oxides in energy storage and conversion systems.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"79 ","pages":"Article 100536"},"PeriodicalIF":9.1,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144513655","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Quaternary transition metal dichalcogenides (M1-xNxX2(1-y)Y2y) for hydrogen evolution: A review on atomic structure, 3D engineering, and electrocatalytic performance","authors":"Rohit Kumar ,&nbsp;Rajni Thakur ,&nbsp;Sahil Kumar ,&nbsp;Shwetharani R ,&nbsp;Bhari Mallana Nagaraja ,&nbsp;Sunil Mehla ,&nbsp;Itika Kainthla","doi":"10.1016/j.progsolidstchem.2025.100532","DOIUrl":"10.1016/j.progsolidstchem.2025.100532","url":null,"abstract":"<div><div>Hydrogen is a clean, efficient, and sustainable alternative to fossil fuels, placing it at the forefront of our energy future. Water electrolysis is more sustainable and eco-friendlier alternative to fossil fuel-based hydrogen production processes. The earth abundance, low cost, high electrocatalytic activities, and stabilities of transition metal dichalcogenides (TMDs) in the hydrogen evolution reaction (HER) set them apart as exceptional electrocatalysts for hydrogen production. Quaternary TMDs have a general formula of M_1-xN_xX_2(1-y)Y_2y, where M and N are transition metals and X and Y are chalcogens. Thus, quaternary TMDs are versatile nanomaterials that exhibit tremendous potential for fine-tuning and optimizing their electrocatalytic performance through composition modulation, as shown by both theoretical and experimental studies. Additionally, additive manufacturing techniques such as 3D printing are emerging as powerful tools for fabricating structurally complex, compositionally tunable TMD-based electrodes with enhanced HER performance. The integration of 3D printing with advanced TMD synthesis methods enables the design of customized electrocatalysts, offering improved charge transport and catalytic activity for sustainable hydrogen production. To delve deeper into the composition-structure-activity relationships that govern the hydrogen evolution performance of quaternary TMDs, this review encapsulates a comprehensive account of the synthesis methods, atomic and electronic structures, properties, and electrocatalytic performance of quaternary TMDs. Furthermore, the unique challenges in using quaternary TMD electrocatalysts and the authors' perspective on their future potential in hydrogen production are elaborated.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"79 ","pages":"Article 100532"},"PeriodicalIF":9.1,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144230023","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}